Novel ethylenic copolymers, compositions and methods of the same

ABSTRACT

The present disclosure relates to novel ethylenic copolymers comprising from 10% to 80% by weight, of at least one monomer of polyethylene glycol (meth)acrylate type, from 20% to 90% by weight, of at least one anionic monomer, and from 0% to 70% by weight, at least one additional nonionic hydrophilic monomer. The disclosure also relates to a composition, such as cosmetic or pharmaceutical compositions, comprising the copolymers and to a method of using the same.

This application claims benefit of U.S. Provisional Application No.60/590,440, filed Jul. 23, 2004, the contents of which are incorporatedherein by reference. This application also claims benefit of priorityunder 35 U.S.C. §119 to French Patent Application No. 04 51512, filedJul. 13, 2004, the contents of which are also incorporated by reference.

The present disclosure relates to novel polymers, to their use, in, forexample, cosmetics, and to compositions comprising them.

It is known to employ polymers in the cosmetics field, and for example,in the hair field, for purposes such as contributing hold or styling tothe hair.

Numerous cosmetic compositions, and for example, hair compositionsreferred to as hair styling compositions, which are provided in the formof aerosols (sprays), gels, foams or shampoos, comprise resins orpolymers.

For example, U.S. Pat. No. 6,193,961 from ISP discloses a homogeneousterpolymer of N-vinyllactam, such as of N-vinylpyrrolidone or ofN-vinylcaprolactam, of dimethylaminoalkyl acrylate or ofdimethylaminoalkylacrylamide and of a polysiloxane monomer.

U.S. Pat. No. 5,502,136 relates to a process for the preparation ofcopolymers of vinylpyrrolidone and of vinyl acetate by radicalpolymerization.

However, it was found that these polymers may not exhibit satisfactoryremoval on shampooing.

In the field of hair compositions referred to as ‘leave-in’compositions, such as styling products of styling spray, gel or lacquertype, there is a continual search for good styling polymers.

For example, International Patent Application Publication WO 2002/09656discloses hydrophobic polymers based on butyl acrylate, which contributea repositionable styling effect. European Patent Application PublicationNo. EP 1 201 223 discloses copolymers based on alkyl (meth)acrylateswhich may make it possible to style and restyle the hair at will.However, in both these cases, the cosmetic quality to the touch may beinadequate.

Thus, it would be desirable to find polymers which provide styling butat the same time also provide at least one acceptable cosmetic qualityand are easily removed on shampooing.

The present disclosure seeks to provide polymers capable of contributinga true styling effect to the compositions, while retaining an acceptablecosmetic quality and for example, good removal on shampooing.

After much research, the present inventors have found that the use ofpolymers comprising, inter alia, monomers of the polyethylene glycol(meth)acrylate type as defined below may make possible the preparationof styling compositions having an appropriate cosmetic quality.

Polymers comprising polyethylene glycol (meth)acrylate (PEGM) units maybe provided for in the prior art.

For example, European Patent Application Publication No. EP 372 546discloses copolymers based on PEGM and on monomers of (C₁-C₈alkyl)(meth)acrylamide type which may comprise cationic monomers. Thesecationic polymers, however, are not always easily removed on rinsing.Furthermore, they may not make it possible to produce suitable cosmeticeffects, such as a deposited layer on the hair, which is sufficient tocontribute the desired properties.

Japanese Patent Application Publication JP2002-322219 discloses polymerscomprising PEGM units in combination with hydrophobic monomers based onpolypropylene glycol (PPO) or on poly(tetramethylene oxide) and cationicmonomers. These polymers thus comprise hydrophobic monomers and they maynot make it possible to obtain satisfactory cosmetic properties.

In addition, Japanese Patent Application Publication JP2002-284627discloses a composition comprising cationic polymers wherein monomers ofPEG type are combined with monomers comprising quaternary amine units.In this instance, the presence of quaternary units may result, duringapplication, in extra deposition, which may lead, in some cases, to apoor cosmetic quality and may result in difficulties in removal onshampooing.

Furthermore, Japanese Patent Application Publication JP2003-055164discloses polymers comprising units of the PEGM type; however, thesepolymers are crosslinked, which may make it difficult to control theirsynthesis and their removal on shampooing.

Japanese Patent Application Publication JP2000-302649 discloses a haircomposition comprising a polymer, which comprises cationic or amphotericmonomers, monomers with a polyether group, such as PEGM or PPO type, andoptional monomers which may be mainly hydrophobic (stearylmethacrylate).

In addition, Japanese Patent No. JP07-285831 also discloses haircompositions comprising a polymer which comprises monomers of PEGM typein combination with ionic, cationic or amphoteric monomers andadditional monomers, mainly hydrophobic, of C₁-C₂₄ alkyl (meth)acrylatetype.

However, the presence of hydrophobic monomers of butyl acrylate orstearyl acrylate type may not make it possible to obtain suitablecosmetic properties, such as a satisfactory good cosmetic quality andsatisfactory removal on shampooing.

International Patent Application Publication WO 03/075867 is also known,which discloses linear block copolymers comprising a poly(alkyleneglycol) block framed by two ethylenic blocks. These polymers may exhibitthe drawback of having a central block of poly(alkylene glycol) typewith a high mass which confers high crystallinity on the polymer, whichmay result in opaque products and/or products exhibiting a greasynature.

Furthermore, in all the polymers disclosed in these documents, the ionicmonomers may be mainly cationic monomers, which may form a depositedlayer on the hair when they are brought into the presence of an anionicsurfactant. In some cases, for example, the case of leave-in stylingproducts of lacquer type, it may be desirable to have availablecompositions which may be easily removed, such as on washing, forexample, with a shampoo comprising an anionic surfactant.

It is thus desirable to have polymers comprising PEGMs and anionic unitsin order to obtain a satisfactory deposited layer of polymer on thehair.

The present disclosure demonstrates novel polymers which may make itpossible to contribute a styling and conditioning effect to haircosmetic products while also being easy to remove, for example, onshampooing.

Surprisingly, the polymers according to the present disclosure havedesirable cosmetic properties, for example, when applied in aformulation of lacquer or shampoo type. For example, it has been foundthat the hair easily disentangles during shampooing and may exhibitsoftness after application; after drying, the compositions according tothe disclosure also may make possible a desirable reshaping of the hair.

In addition, the application of these presently disclosed compositionsmay make it possible to obtain a styling effect, which may be easilyremoved on shampooing.

Finally, the polymers according to the disclosure may be easilyformulated, for example, in a pump-action spray.

Without being committed to the present explanation, it may be thoughtthat these properties may, for example, be due to the presence of PEG(meth)acrylate (PEGM) units within the polymer chain, which unitslargely contribute to the effect obtained.

The present disclosure thus relates to an ethylenic copolymercomprising:

a) from 10% to 80% by weight, relative to the total weight of thecopolymer, of at least one monomer of formula (I) as defined below;

b) from 20% to 90% by weight, relative to the total weight of thecopolymer, of at least one anionic monomer chosen from maleic anhydrideand monomers of formula (II) as defined below, and

c) optionally from 0% to 70% by weight, relative to the total weight ofthe copolymer, of at least one nonionic hydrophilic monomer.

Another embodiment of the present disclosure is a compositioncomprising, in a physiologically acceptable medium, at least one suchcopolymer.

The polymers disclosed herein may generally be conveyed in water, thatis to say which are soluble or dispersible in water, which may make itpossible to employ them in cosmetic compositions, such as skin care orhair compositions, generally with an aqueous base.

As used herein, the term “water-soluble” or “soluble in water” isunderstood to mean that the polymer forms a clear solution in water, ina proportion of at least 5% by weight, at 25° C.

As used herein, the term “water-dispersible” or “dispersible in water”means that the polymer forms in water, at a concentration of 5% byweight, at 25° C., a stable suspension or dispersion of fine, generallyspherical, particles. The mean size of the particles constituting thedispersion may be, for example, less than 1 μm and, more generally,ranges from 5 nm to 400 nm, such as from 10 nm to 250 nm. These particlesizes may be measured by light scattering techniques.

As used herein, the term “cyclic radical” refers to a monocyclic orpolycyclic radical which may itself exist in the form of at least onering chosen from saturated and unsaturated rings which are optionallysubstituted (for example, cyclohexyl, cyclodecyl, benzyl or fluorenyl)but also a radical which comprises at least one of the rings (forexample, p-(tert-butyl)cyclohexyl or 4-hydroxybenzyl).

As used herein, the term “saturated and/or unsaturated radical” refersto fully saturated radicals, fully unsaturated radicals, includingaromatic radicals, and radicals comprising at least one bond chosen fromdouble and triple bonds, the remainder of the bonds being single bonds.

The ethylenic copolymer according to the present disclosure thuscomprises at least one monomer of formula (I), which may be presentalone or as a mixture:

wherein:

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbonradicals C_(p)H_(2p+1) wherein p is an integer ranging from 1 to 12inclusive;

Z is a divalent group chosen from —COO—, —CONH—, —CONCH₃—, —OCO—, —O—,—SO₂—, —CO—O—CO—, and —CO—CH₂—CO—;

x is chosen from 0 and 1;

R₂ is chosen from linear, branched and cyclic, saturated andunsaturated, optionally aromatic, divalent hydrocarbon radicals havingfrom 1 to 30 carbon atoms which optionally comprise from 1 to 18heteroatoms chosen from O, N, S, F, Si, and P;

m is chosen from 0 and 1;

n is an integer ranging from 3 to 300 inclusive;

R₃ is chosen from a hydrogen atom and linear, branched and cyclic,saturated and unsaturated, optionally aromatic, hydrocarbon radicalshaving from 1 to 30 carbon atoms, which optionally comprises from 1 to20 heteroatoms chosen from O, N, S, F, Si, and P; and salts thereof.

For example, in at least one embodiment, R₁ is chosen from methyl,ethyl, propyl, and butyl radicals. In at least one further embodiment,R₁ is chosen from hydrogen and a methyl radical.

In at least one embodiment, Z is chosen from —COO— and —CONH—.

In at least one embodiment, x is equal to 1.

In the R₂ radical, the heteroatom or heteroatoms, when they are present,may be inserted into the chain of the R₂ radical or the R₂ radical maybe substituted by at least one group comprising them, such as hydroxylor amino (NH₂, NHR′ or NR′R″, with R′ and R″; which may be identical ordifferent, chosen from linear and branched C₁-C₂₂ alkyls, such as methylor ethyl).

For example, R₂ comprises a radical chosen from:

an alkylene radical, such as methylene, ethylenic, propylene,n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene,n-dodecylene, n-octadecylene, n-tetradecylene or n-docosenylene;

a phenylene radical —C₆H₄— (ortho, meta or para) optionally substitutedby a C₁-C₁₂ alkyl radical optionally comprising from 1 to 25 heteroatomschosen from O, N, S, F, Si, and P; or a benzylene radical —C₆H₄—CH₂—optionally substituted by a C₁-C₁₂ alkyl radical optionally comprisingfrom 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P;

a pyridinium radical of formula:

wherein R′₁ to R′₄, which may be identical or different, are chosen fromH and C₁-C₁₂ alkyl radicals optionally comprising from 1 to 8heteroatoms chosen from O, N, S, F, Si, and P; in at least oneembodiment, R′₁ to R′₄ may independently be chosen from methyl andethyl;

a radical of formula —CH₂—O—CO—O—, —CH₂—CH₂—O—CO—O—, —CH₂—CO—O—,—CH₂—CH₂—CO—O—, —CH₂—O—CO—NH—, —CH₂—CH₂—O—CO—NH—; —CH₂—NH—CO—NH— and—CH₂—CH₂—NH—CO—NH—, —CH₂—CHOH—, —CH₂—CH₂—CHOH—, —CH₂—CH₂—CH(NH₂)—,—CH₂—CH(NH₂)—, —CH₂—CH₂—CH(NHR′)—, —CH₂—CH(NHR′)—, —CH₂—CH₂—CH(NR′R″)—,—CH₂—CH(NR′R″)—, —CH₂—CH₂—CH₂—NR′—, —CH₂—CH₂—CH₂—O—, and—CH₂—CH₂—CHR′—O— wherein R′ and R″ are chosen from linear and branchedC₁-C₂₂ alkyls optionally comprising from 1 to 12 heteroatoms chosen fromO, N, S, F, Si, and P;

and mixtures thereof.

For example, in at least one embodiment, n ranges from 5 and 200inclusive and further for example, from 7 to 100 inclusive, such as from9 to 50 inclusive.

Further for example, in at least one embodiment, R₃ is chosen from ahydrogen atom; benzyl and phenyl radicals optionally substituted by aC₁-C₁₂ alkyl radical optionally comprising from 1 to 25 heteroatomschosen from O, N, S, F, Si, and P; and C₁-C₃₀, such as C₁-C₂₂, furtherfor example, C₂-C₁₆, alkyl radicals optionally comprising from 1 to 18heteroatoms chosen from O, N, S, F, Si, and P.

These benzyl, phenyl and alkyl radicals optionally comprise, forexample, a functional group chosen from the following functional groups:

or else chosen from —SO₃H, —COOH, —PO₄, —NR₅R₆, and —N⁺R₅R₆R₇, whereinR₅, R₆ and R₇ are chosen, independent of one another, from H and fromlinear, branched and cyclic C₁-C₁₈ alkyls, such as methyl, optionallycomprising at least one heteroatom and also carrying protective groups,such as t-butyloxycarbonyl (also known as BOC) and9-fluorenylmethoxycarbonyl (also known as FmoC).

Mention may be made, among the R₃ radicals, for example, of the methyl,ethyl, propyl, benzyl, ethylhexyl, lauryl, stearyl, or behenyl(—(CH₂)₂₁—CH₃) chains and also fluorinated alkyl chains, such as, forexample, heptadecafluorooctylsulphonylaminoethylCF₃—(CF₂)₇—SO₂—N(C₂H₅)—CH₂—CH₂; or —CH₂—CH₂—CN, succinimido, maleimido,mesityl, tosyl, triethoxysilyl or phthalimido chains.

The amine units of the monomer may optionally be neutralized.

Mention may be made, among the salts, for example, of the salts ofinorganic acids, such as sulphuric acid, hydrochloric acid, hydrobromicacid, hydriodic acid, phosphoric acid or boric acid. Mention may also bemade, for example, of the salts of organic acids, which optionallycomprise at least one carboxylic, sulphonic or phosphonic acid group.They may be linear, branched or cyclic aliphatic acids or aromaticacids. These acids may additionally comprise at least one heteroatomchosen from O and N, for example in the form of hydroxyl groups. Mentionmay, for example, be made of propionic acid, acetic acid, terephthalicacid, citric acid, and tartaric acid.

The acid groups may be neutralized with an inorganic base, such as LiOH,NaOH, KOH, Ca(OH)₂, NH₄OH, Mg(OH)₂ or Zn(OH)₂; or with an organic base,such as a primary, secondary or tertiary alkylamine, for exampletriethylamine or butylamine. This primary, secondary or tertiaryalkylamine may comprise at least one nitrogen and/or oxygen atom and maythus comprise, for example, at least one alcohol functional group;mention may, for example, be made of 2-amino-2-methylpropanol,triethanolamine and 2-(dimethylamino)propanol. Mention may also be made,for example, of lysine or 3-(dimethylamino)propylamine.

Mention may be made, for example, among the monomers of formula (I) of:

polyethylene glycol (meth)acrylate, wherein R₁ is chosen from H andmethyl, Z is COO, x=1, m=0, and R₃═H;

methylpolyethylene glycol (meth)acrylate, also known asmethoxypolyethylene glycol (meth)acrylate, wherein R₁ is chosen from Hand methyl, Z is COO, x=1, m=0, and R₃=methyl;

alkylpolyethylene glycol (meth)acrylates, wherein R₁ is chosen from H ormethyl, Z is COO, x=1, m=0, and R₃=alkyl;

phenylpolyethylene glycol (meth)acrylate, also known as polyethyleneglycol phenyl ether (meth)acrylate, wherein R₁ is chosen from H andmethyl, Z is COO, x=1, m=0, and R₃=phenyl;

the following monomer:

wherein n ranges from 3 to 100 inclusive, such as from 5 to 50inclusive, for example, from 7 to 30 inclusive.

Examples of commercial monomers are:

CD 350 (methoxypolyethylene glycol 350 methacrylate) and CD 550(methoxypolyethylene glycol 550 methacrylate), supplied by SartomerChemicals;

M90G (methoxypolyethylene glycol (9 repeat units) methacrylate) andM230G (methoxypolyethylene glycol (23 repeat units) methacrylate),available from Shin-Nakamura Chemicals;

methoxypolyethylene glycol methacrylates with mean molecular weights of300, 475, or 1100, available from Sigma-Aldrich;

methoxypolyethylene glycol acrylate with a mean molecular weight of 426,available from Sigma-Aldrich;

methoxypolyethylene glycol methacrylates, available from Laporte underthe trade names: MPEG 350, MPEG 550, S10W, and S20W;

polyethylene glycol monomethyl ether, mono(succinimidyl succinate)ester, products with a mean molecular weight of 1900 or 5000, fromPolysciences;

behenylpolyethylene glycol PEG-25 methacrylate, available from Rhodiaunder the name Sipomer BEM;

polyethylene glycol phenyl ether acrylates with mean molecular weightsof 236, 280, or 324, available from Aldrich;

methoxypolyethylene glycol 5000 2-(vinylsulphonyl)ethyl ether, availablecommercially from Fluka;

polyethylene glycol ethyl ether methacrylate, available from Aldrich;and

polyethylene glycol 8000, 4000, and 2000 methacrylates, fromMonomer-Polymer & Dajac Laboratories.

The at least one monomer of formula (I), alone or as a mixture, ispresent in an amount ranging from 10% to 80% by weight, relative to thetotal weight of the copolymer, such as from 20% to 70% by weight, forexample, from 30% to 60% by weight, relative to the total weight of thecopolymer.

The ethylenic copolymer according to the present disclosure alsocomprises at least one anionic monomer, and salts thereof, chosen frommaleic anhydride and monomers of formula (II).

As used herein, the term “anionic monomer” refers to a monomer, whichmay carry a negative charge ranging from pH 4 to pH 12.

The monomers may thus be of formula:

wherein:

R₁ is chosen from a hydrogen atom and linear and branched hydrocarbonradicals C_(p)H_(2p+1) wherein p is an integer between 1 and 12inclusive; in at least one embodiment, for example, R₁ is chosen frommethyl, ethyl, propyl, and butyl radicals. In another embodiment, R₁ ischosen from hydrogen and a methyl radical.

Z′ is a divalent group chosen from —COO—, —OCO— and —O—, —SO₂—,—CO—O—CO—, and —CO—CH₂—CO—; in at least one embodiment, Z′ is —COO—;

x′ is chosen from 0 or 1, for example 1;

R₂′ is chosen from linear, branched and cyclic, saturated andunsaturated, optionally aromatic, divalent hydrocarbon radicals havingfrom 1 to 30 carbon atoms which may comprise from 1 to 18 heteroatomschosen from O, N, S, F, Si, and P;

In the R₂′ radical, the heteroatom or heteroatoms, when they arepresent, may be inserted into the chain of the R₂′ radical or the R₂′radical may be substituted by at least one group comprising them, suchas hydroxyl.For example, in at least one embodiment, R₂′ comprises:

an alkylene radical, such as methylene, ethylenic, propylene,n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene,n-dodecylene, n-octadecylene, n-tetradecylene or n-docosenylene;

a phenylene radical —C₆H₄— (ortho, meta or para) optionally substitutedby a C₁-C₁₂ alkyl radical optionally comprising from 1 to 25 heteroatomschosen from N, O, S, F, Si and/or P; or a benzylene radical —C₆H₄—CH₂—optionally substituted by a C₁-C₁₂ alkyl radical optionally comprisingfrom 1 to 25 heteroatoms chosen from O, N, S, F, Si, and P;

a radical of formula —CH₂—O—CO—O—, —CH₂—CH₂—O—CO—O—, —CH₂—CO—O—,—CH₂—CH₂—CO—O—, —CH₂—O—CO—NH—, —CH₂—CH₂—O—CO—NH—, —CH₂—NH—CO—NH—,—CH₂—CH₂—NH—CO—NH—, —CH₂—CHOH—, CH₂—CH₂—CHOH—, CH₂—CH₂—CH—O—, and—CH₂—CH₂—CHR′—O— wherein R′ is chosen from a linear and branched C₁-C₂₂alkyl radicals optionally comprising from 1 to 12 heteroatoms chosenfrom O, N, S, F, Si and P; and mixtures thereof.

m′ is chosen from 0 and 1;

Y is a group chosen from —COOH, —SO₃H, —OSO₃H, —PO₃H₂, and —OPO₃H₂.

The acid groups may be neutralized with an inorganic or organic base asindicated above.

It is understood that, according to the state of the art, the SO₄H andPO₄H₂ groups are bonded to R₂′ via the oxygen atom, whereas the SO₃H andPO₃H₂ groups are bonded to R₂′ via the S and P atoms respectively.

Mention may be made, among the anionic monomers useful herein, forexample, of maleic anhydride, acrylic acid, methacrylic acid, crotonicacid, itaconic acid, fumaric acid, maleic acid, 2-carboxyethyl acrylate(CH₂═CH—C(O)—O—(CH₂)₂—COOH), styrenesulphonic acid, vinylbenzoic acid,vinylphosphonic acid, sulphopropyl (meth)acrylate, sulphatoethyl(meth)acrylate, and salts thereof, such as the ammonium salts.

The at least one anionic monomer, alone or as a mixture, is present inthe composition of the present disclosure in an amount ranging from 20%to 90% by weight, relative to the total weight of the copolymer, such asfrom 30% to 80% by weight, and for example, from 40% to 70% by weight,relative to the total weight of the copolymer.

The ethylenic copolymer according to the present disclosure mayoptionally comprise other additional monomers than those mentionedabove. When it comprises such other additional monomers, the latter arenecessarily chosen from nonionic monomers, which are to be hydrophilicwithin the meaning of the present disclosure.

As used herein, the term “hydrophilic monomer” refers to monomers havinga value of the logarithm of the 1-octanol/water apparent partitioncoefficient, also referred to as log P, of less than or equal to 2, forexample from −8 to 2, such as less than or equal to 1.5, for example,less than or equal to 1, and further for example, from −7 to 1, such asfrom −6 to 0.

The log P values are known and may be determined according to a standardtest, which determines the concentration of the monomer in the octanoland the water.

The values may, for example, be calculated using the ACD (AdvancedChemistry Development) Software Solaris V4.67 software; they may also beobtained from Exploring QSAR: hydrophobic, electronic and stericconstants (ACS professional reference book, 1995).

There also exists an Internet site, which provides estimated values(address: http//esc.syrres.com/interkow/kowdemo.htm).

The log P values for some standard monomers, determined using the ACDsoftware, are shown below:

Methacrylate Acrylate (* or (* or methacrylamide) acrylamide) Methyl(meth)acrylate 1.346 ± 0.250 0.793 ± 0.223 Ethyl (meth)acrylate 1.877 ±0.250 1.325 ± 0.223 Propyl (meth)acrylate 2.408 ± 0.250 1.856 ± 0.223Isopropyl (meth)acrylate 2.224 ± 0.254 1.672 ± 0.228 Butyl(meth)acrylate 2.940 ± 0.250 2.387 ± 0.223 Isobutyl (meth)acrylate 2.756± 0.254 2.208 ± 0.228 tert-Butyl (meth)acrylate 2.574 ± 0.261 2.022 ±0.238 Cyclohexyl (meth)acrylate 3.405 ± 0.252 2.853 ± 0.226 Octyl(meth)acrylate 5.065 ± 0.521 4.513 ± 0.224 Lauryl (meth)acrylate 7.190 ±0.251 6.638 ± 0.224 Tridecyl (meth)acrylate 7.712 ± 0.251 7.170 ± 0.224Cetyl (meth)acrylate 9.316 ± 0.251 8.764 ± 0.224 Palmityl(meth)acrylate >9 >9 Stearyl (meth)acrylate 10.379 ± 0.251  9.826 ±0.224 Behenyl (meth)acrylate 11.952 ± 0.225  12.504 ± 0.251  Oleyl(meth)acrylate >9 9.308 ± 0.232 Tetrahydrofurfuryl (meth)acrylate 1.352± 0.283 0.800 ± 0.263 2-Ethylhexyl (meth)acrylate 4.881 ± 0.254 4.329 ±0.229 2-Hydroxyethyl (meth)acrylate 0.718 ± 0.277 0.166 ± 0.258Ethoxyethyl (meth)acrylate 1.887 ± 0.293 1.335 ± 0.268 Hydroxypropyl(meth)acrylate 0.383 ± 0.241 N-Isopropyl(meth)acrylamide* 0.748 ± 0.2760.195 ± 0.256 N-Octyl(meth)acrylamide* 3.558 ± 0.273 3.036 ± 0.253N,N-Dimethyl(meth)acrylamide* 0.906 ± 0.553 −0.168 ± 0.556 N,N-Dibutyl(meth)acrylamide* 3.573 ± 0.570 3.021 ± 0.557 Vinyl acetate0.730 ± 0.286 Methyl vinyl ether 0.509 ± 0.286 Ethyl vinyl ether 1.040 ±0.286 Vinylcaprolactam 1.499 ± 0.207 Vinylpyrrolidone 0.370 ± 0.206N-Vinylacetamide    0 ± 0.231

The additional, hydrophilic monomers may, for example, be chosen fromthose of formula (III), alone or as a mixture:

wherein:

R′₁ is chosen from hydrogen and —CH₃;

Z″ is a divalent group chosen from —COO—, —CONH—, —CONCH₃—, —OCO—,—SO₂—, —CO—O—CO—, —CO—CH₂—CO— and —O—; in at least one embodiment, forexample, Z is chosen from —COO— and —CONH—;

x″ is chosen from 0 and 1;

R″ is chosen from linear, branched and cyclic, saturated andunsaturated, optionally aromatic, hydrocarbon radicals having from 1 to30 carbon atoms, which optionally comprise from 1 to 18 heteroatomschosen from O, N, S, F, Si, and P.

In the R″ radical, the heteroatom or heteroatoms, when they are present,may be inserted into the chain of the radical or the radical may besubstituted by at least one group comprising them, such as hydroxyl,ester, amide, urethane or urea. For example, R″ may chosen from methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, benzyland furfuryl radicals and radicals of formula —CH₂—CH₂—CH₂OH,—CH₂—CH₂—OH and —CH₂—CH₂—CH₂—OH.

The at least one additional nonionic hydrophilic monomer is chosen, forexample, from the following monomers: methyl methacrylate, methylacrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, isopropylacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate,2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethoxyethylmethacrylate, ethoxyethyl acrylate, N-isopropylacrylamide,N-isopropylmethacrylamide, N,N-dimethylacrylamide,N,N-dimethylmethacrylamide, vinyl acetate, methyl vinyl ether, ethylvinyl ether, vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide,hydroxypropyl acrylate, N-vinyllactam, acrylamide, N-methylacrylamide,N,N-dimethylacrylamide, N-methyl-N-vinylacetamide, N-vinylformamide,N-methyl-N-vinylformamide, and vinyl alcohol (copolymerized in the vinylacetate form and then hydrolyzed).

The at least one additional nonionic hydrophilic monomer, alone or as amixture, may not be present in the copolymer according to the disclosure(e.g., 0% by weight) or else may be present in an amount ranging up to70% by weight, relative to the total weight of the copolymer; forexample, it may be present in an amount ranging from 0.1% to 35% byweight, such as from 1% to 25% by weight, for example of 3 to 15% byweight, and further for example, from 5% to 9.5% by weight, relative tothe total weight of the copolymer.

The copolymer is, for example, a polymer comprising an overall negativecharge, although it may comprise possible amine units.

The copolymers according to the disclosure may be prepared according tostandard conventional radical polymerization methods well known to thoseskilled in the art and as described, for example, in the work “Chimie etphysico-chimie des polymères” [Chemistry and Physical Chemistry ofPolymers]”, by Gnanou et al. (published by Dunod).

For example, these copolymers may be prepared by:

direct polymerization in solution in water, with or withoutpreneutralization of the anionic unit;

polymerization as an emulsion in water, with or withoutpreneutralization of the anionic unit and with use of a surfactant;and/or polymerization in an organic solvent, such as ethanol or methylethyl ketone, with or without preneutralization of the anionic unit,followed by a stage of dissolving or dispersing in water withevaporation of the solvent.

These polymerizations may be carried out in the presence of a radicalinitiator, for example, of peroxide type (Trigonox 21S: tert-butylperoxy-2-ethylhexanoate) or azo type (AIBN V50:2,2′-azobis(2-amidinopropane)dihydrochloride), which may be present inan amount ranging from 0.3% to 5% by weight, relative to the totalweight of the copolymer.

The copolymers according to the disclosure are noncrosslinked. They areprovided in the form of random ethylenic copolymers, which are, forexample, film-forming, of at least one ethylenic monomer comprising PEGgroups (the PEG groups may be pendent along the backbone) and of atleast one ethylenic monomer comprising anionic functional groups andoptionally at least one other monovalent nonionic hydrophilic ethyleniccomonomer.

As used herein, the term “‘ethylenic’ polymer” refers to a polymerobtained by polymerization of monomers comprising an ethylenicunsaturation.

As used herein, the term “‘film-forming’ polymer” refers to a polymercapable of forming, by itself alone or in the presence of an additionalagent which is able to form a film, a continuous and adherent film on asupport, such as on keratinous substances.

The copolymers of the present disclosure exhibit a weight-averagemolecular mass (Mw) which ranges, for example, from 500 and 5,000,000,such as from 1000 to 3,000,000 and further for example, from 2000 to2,000,000, such as from 4000 to 500,000, inter alia, from 7000 to250,000, such as from 8000 to 100,000.

The weight-average molar masses (Mw) may be determined by gel permeationchromatography or by light scattering, according to how accessible themethod is, e.g., considering the solubility of the polymers.

The polymers according to the present disclosure may, for example, beconveyed in an aqueous medium, that is to say that they arewater-soluble or water-dispersible.

Dissolving or dispersing in water may be carried out by directdissolution of the polymer, if it is soluble, or else by neutralizationof the acid units, so as to render the polymer soluble or dispersible inwater.

Dissolving or dispersing in an aqueous medium may also be carried outvia an intermediate stage of dissolution in an organic solvent, followedby the addition of water, before evaporation of the organic solvent.

Furthermore, the polymers according to the present disclosure, forexample, may exhibit a viscosity in water which is suitable for theapplications envisaged and which may be, for example, range from 1 mPa·sto 1000 mPa·s, such as from 1.5 mPa·s to 750 mPa·s and further forexample, from 2 mPa·s to 500 mPa·s.

The viscosity may be measured using a Brookfield viscometer for a 15% byweight solution of polymer in water or methyl ethyl ketone (solventchosen according to the solubility of the polymer and/or thepolymerization method) at 25° C. with a rotor of spindle type chosenfrom the Brookfield models numbered 00 to 07, such as rotor No. 1, for ameasuring time of 5 minutes, at a speed of between 0.1 and 6revolutions/minute, for example, 6 revolutions/minute. The viscosity ismeasured after complete dissolution of the polymer in water or methylethyl ketone.

A person skilled in the art may choose the rotor on the basis of generalknowledge known in the art. The speed may also chosen so as to be ableto carry out the measurement within an acceptable range of accuracy forliquid compounds which are not very viscous.

In addition, the copolymers according to the disclosure, for example,exhibit a glass transition temperature (Tg) ranging from −150° C. to 20°C., such as from −120° C. to 10° C., further for example, from −100° C.to 00° C.; the Tg is measured according to the method given before theexamples.

The polymers according to the disclosure may also, for example, exhibita melting point (M.p.) ranging from −100° C. to 80° C., such as from−80° C. to 50° C., further for example, from −70° C. and 45° C., such asfrom −10° C. to 25° C.

In addition, the copolymers according to the disclosure, for example,exhibit a water uptake ranging from 3% to 150% by weight, such as from4% to 120% by weight, further for example, from 4.5% to 90% by weight,at 75% relative humidity (75% RH); the water uptake may be measuredaccording to the method given before the examples.

They may also exhibit a water uptake ranging from 5% to 90% by weight,such as from 7.5% to 75% by weight, further for example, from 15% to 60%by weight, at 85% relative humidity (85% RH).

The copolymers according to the disclosure may be used in the field ofcosmetics. They may also be present in the composition in the dissolvedform, for example dissolved in water or an organic solvent, or else inthe form of an aqueous or organic dispersion.

They may be used in cosmetic or pharmaceutical compositions in an amountranging from 0.01% to 50% by weight on a dry basis, such as from 0.1% to30% by weight, for example, from 1% to 25% by weight, such as from 3% to20% by weight, relative to the total weight of the copolymer.

The cosmetic or pharmaceutical compositions according to the disclosurecomprise, in addition to the polymers, a physiologically acceptablemedium, such as a cosmetically or dermatologically acceptable medium,that is to say a medium compatible with keratinous substances, such asthe skin of the face or body, the hair, the eyelashes, the eyebrows, andthe nails.

The composition may thus comprise a hydrophilic medium comprising wateror a mixture of water and at least one hydrophilic organic solvent, suchas alcohols and for example, linear or branched C₁-C₆ monoalcohols, suchas ethanol, tert-butanol, n-butanol, isopropanol or n-propanol, andpolyols, such as glycerol, diglycerol, propylene glycol, sorbitol,pentylene glycol and polyethylene glycols, or alternatively glycolethers, such as C₂ glycol ethers, and C₂-C₄ aldehydes which arehydrophilic.

The water or the mixture of water and at least one hydrophilic organicsolvent may be present in the composition according to the disclosure inan amount ranging from 0.1% to 99% by weight, relative to the totalweight of the composition, and for example, from 10% to 80% by weight.

The composition can also comprise a fatty phase, composed, for example,of fatty substances which may be liquid at ambient temperature (25° C.in general) and/or of fatty substances, which are solid at ambienttemperature, such as waxes, pasty fatty substances, gums and theirmixtures. These fatty substances may be of animal, vegetable, mineral,or synthetic origin. This fatty phase may additionally comprise at leastone lipophilic organic solvent.

Mention may be made, as fatty substances which are liquid at ambienttemperature, often known as oils, which may be used in the disclosure,for example, of: hydrocarbon oils of animal origin, such asperhydrosqualene; vegetable hydrocarbon oils, such as liquidtriglycerides of fatty acids comprising 4 to 10 carbon atoms, such astriglycerides of heptanoic or octanoic acids, or sunflower, maize,soybean, grape seed, sesame, apricot, macadamia, castor or avocado oils,triglycerides of caprylic/capric acids, jojoba oil or shea butter oil;linear or branched hydrocarbons of mineral or synthetic origin, such asliquid paraffins and their derivatives, liquid petrolatum, polydecenesor hydrogenated polyisobutene, such as parieam; synthetic esters andethers, for example, of fatty acids, such as, purcellin oil, isopropylmyristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate,2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters,such as isostearyl lactate, octyl hydroxystearate, octyldodecylhydroxystearate, diisostearyl malate, triisocetyl citrate orheptanoates, octanoates or decanoates of fatty alcohols; polyol esters,such as propylene glycol dioctanoate, neopentyl glycol diheptanoate ordiethylene glycol diisononanoate; pentaerythritol esters; fatty alcoholshaving from 12 to 26 carbon atoms, such as octyldodecanol,2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol or oleyl alcohol;partially hydrocarbon-comprising and/or silicone-comprising fluorinatedoils; silicone oils, such as volatile or nonvolatile and linear orcyclic polymethylsiloxanes (PDMS) which are liquid or pasty at ambienttemperature, such as cyclomethicones, dimethicones, optionallycomprising a phenyl group, such as phenyl trimethicones,phenyltrimethylsiloxydiphenylsiloxanes,diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyldimethicones or polymethylphenylsiloxanes; and mixtures thereof.

These oils may be present in an amount ranging from 0.01% to 90% byweight, and for example, from 0.1% to 85% by weight, relative to thetotal weight of the composition.

The composition according to the disclosure may also comprise at leastone physiologically acceptable organic solvent.

These solvents may generally be present in an amount ranging from 0.1%to 90% by weight, such as from 0.5% to 85% by weight, for example from10 to 80% by weight, relative to the total weight of the composition,and further for example, from 30% to 50% by weight.

Mention may, for example, be made, in addition to the hydrophilicorganic solvents mentioned above, of ketones which are liquid at ambienttemperature, such as methyl ethyl ketone, methyl isobutyl ketone,diisobutyl ketone, isophorone, cyclohexanone or acetone; propyleneglycol ethers which are liquid at ambient temperature, such as propyleneglycol monomethyl ether, propylene glycol monomethyl ether acetate ordipropylene glycol mono(n-butyl)ether; short-chain esters (having from 3to 8 carbon atoms in total), such as ethyl acetate, methyl acetate,propyl acetate, n-butyl acetate or isopentyl acetate; ethers which areliquid at 25° C., such as diethyl ether, dimethyl ether ordichlorodiethyl ether; alkanes which are liquid at 25° C., such asdecane, heptane, dodecane, isododecane or cyclohexane; cyclic aromaticcompounds which are liquid at 25° C., such as toluene and xylene; andaldehydes which are liquid at 25° C., such as benzaldehyde oracetaldehyde, and their mixtures.

As used herein, the term “wax” within the meaning of the presentdisclosure refers to a lipophilic compound, solid at ambient temperature(25° C.), with a reversible solid/liquid change of state, having amelting point of greater than or equal to 25° C. which may range up to120° C. On bringing the wax to the liquid state (melting), it ispossible to render it miscible with the oils possibly present and toform a microscopically homogeneous mixture but, on bringing thetemperature of the mixture back to ambient temperature,recrystallization of the wax from the oils of the mixture may beobtained. The melting point of the wax may be measured using adifferential scanning calorimeter (DSC), for example the calorimetersold under the name DSC 30 by Mettler.

The waxes may be hydrocarbon, fluorinated and/or silicone waxes and maybe of vegetable, mineral, animal and/or synthetic origin. For example,the waxes exhibit a melting point of greater than 30° C., such asgreater than 45° C. Mention may be made, as wax which may be used in thecomposition of the disclosure, for example, of beeswax, carnauba wax,candelilla wax, paraffin wax, microcrystalline waxes, ceresin orozokerite; synthetic waxes, such as polyethylene or Fischer-Tropschwaxes, or silicone waxes, such as alkyl or alkoxy dimethicones havingfrom 16 to 45 carbon atoms.

The gums may be generally high molecular weight polydimethylsiloxanes(PDMSs) or cellulose gums or polysaccharides and the pasty substancesare generally hydrocarbon compounds, such as lanolins and theirderivatives, or PDMSs.

The nature and the amount of the solid substances depend on the desiredmechanical properties and the desired textures. By way of example, thecomposition may comprise from 0.1% to 50% by weight of waxes, relativeto the total weight of the composition, and further for example, from 1to 30% by weight.

The composition according to the disclosure may additionally comprise,in a particulate phase, pigments and/or pearlescent agents and/orfillers commonly used in cosmetic compositions.

The composition may also comprise other coloring materials chosen fromwater-soluble dyes or fat-soluble dyes well known to a person skilled inthe art.

As used herein, the term “pigments” refers to white or colored andinorganic or organic particles of any shape which may be insoluble inthe physiological medium and which may be intended to color thecomposition.

As used herein, the term “fillers” refers to colorless or white,inorganic or synthetic and lamellar or nonlamellar particles which maybe intended to give body or stiffness to the composition and/orsoftness, mattness and uniformity to the makeup.

As used herein, the term “pearlescent agents” refers to iridescentparticles of any shape produced such as by certain shellfish in theirshells or else synthesized.

The pigments may be present in the composition in an amount ranging from0.01% to 25% by weight, relative to the total weight of the compositionand for example, ranging from 3% to 10% by weight. They may be white orcolored and inorganic or organic. Mention may be made, for example, oftitanium, zirconium or cerium oxides, zinc, iron or chromium oxides,ferric blue, chromium hydrate, carbon black, ultramarines(aluminosilicate polysulphides), manganese pyrophosphate and some metalpowders, such as those of silver or of aluminium. Mention may also bemade, for example, of D&C pigments and lakes, commonly employed toconfer a makeup effect on the lips and skin, which are calcium, barium,aluminium, strontium, or zirconium salts.

The pearlescent agents may be present in the composition in an amountranging from 0.01% to 20% by weight, such as ranging from 3% to 10% byweight, relative to the total weight of the composition. Mention may bemade, among the pearlescent agents, which may be envisaged, for example,of natural mother-of-pearl, mica covered with titanium oxide, with ironoxide, with natural pigment or with bismuth oxychloride, and colouredtitanium oxide-coated mica.

Mention may be made, among fat-soluble or water-soluble dyes, which maybe present in the composition, alone or as a mixture, in an amountranging from 0.001% to 15% by weight, such as from 0.01% to 5% by weightand for example, from 0.1% to 2% by weight, relative to the total weightof the composition, for example, of the disodium salt of ponceau, thedisodium salt of alizarin green, quinoline yellow, the trisodium salt ofamaranth, the disodium salt of tartrazine, the monosodium salt ofrhodamine, the disodium salt of fuchsin, xanthophyll, methylene blue,cochineal carmine, haloacid, azo or anthraquinone dyes, copper sulphate,iron sulphate, Sudan brown, Sudan red and annatto, and sugarbeet juiceand carotene.

The composition according to the disclosure may additionally comprise atleast one filler, such as in an amount ranging from 0.01% to 50% byweight, relative to the total weight of the composition, for example,ranging from 0.02% to 30% by weight. The at least one filler may beinorganic or organic and of any shape, platelet, spherical or oblong.Mention may be made, for example, of talc, mica, silica, kaolin,polyamide (Nylon®) powders, poly(β-alanine) powders, polyethylenepowders, tetrafluoroethylene polymer (Teflon®) powders, lauroyllysine,starch, boron nitride, polymeric hollow microspheres, such as those ofpoly(vinylidene chloride)/acrylonitrile, for example Expancel® (NobelIndustrie), of acrylic acid copolymers (Polytrap® from Dow Corning) andsilicone resin microbeads (Tospearls® from Toshiba, for example),particles of polyorganosiloxane elastomers, precipitated calciumcarbonate, magnesium carbonate and basic magnesium carbonate,hydroxyapatite, hollow silica microspheres (Silica Beads® fromMaprecos), glass or ceramic microcapsules, or metal soaps derived fromorganic carboxylic acids having from 8 to 22 carbon atoms, such as from12 to 18 carbon atoms, for example zinc stearate, magnesium stearate,lithium stearate, zinc laurate or magnesium myristate.

The composition may furthermore comprise an additional polymer, such asa film-forming polymer. According to the present disclosure, the term“film-forming polymer” includes a polymer capable of forming, by itselfalone or in the presence of an additional agent which is able to form afilm, a continuous and adherent film on a support, such as on keratinoussubstances. Mention may be made, among the film-forming polymers capableof being used in the composition of the present disclosure, for example,of synthetic polymers of radical type or of polycondensate type,polymers of natural origin and mixtures thereof, such as acrylicpolymers, polyurethanes, polyesters, polyamides, polyureas or cellulosepolymers, such as nitrocellulose.

The composition may also comprise at least one surface-active agent,which is present in an amount ranging from 0.01% to 50% by weight, suchas from 0.1% to 40% and further for example, from 0.5% to 30%, relativeto the total weight of the composition.

The at least one surface-active agent may be chosen from anionic,amphoteric, nonionic and cationic surface-active agents, and mixturesthereof.

The at least one surfactant, i.e., the at least one surface-activeagent, which is suitable for implementing the present disclosure are,for example, alone or as a mixture:

anionic surfactants, among which may be mentioned, alone or as mixtures,the salts (e.g., alkali metal, such as sodium, salts, ammonium salts,amine salts, aminoalcohol salts or magnesium salts) of the followingcompounds: alkyl sulfates, alkyl ether sulfates, alkylamido ethersulfates, alkylarylpolyether sulfates, monoglyceride sulfates;alkylsulfonates, alkyl phosphates, alkylamidesulfonates,alkylarylsulfonates, α-olefinsulfonates, paraffinsulfonates; alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates;alkyl sulfosuccinamates; alkyl sulfoacetates; alkyl ether phosphates;acylsarcosinates; acylisethionates and N-acyltaurates, the alkyl or acylradical of all these different compounds, for example, comprising from 8to 24 carbon atoms, and the aryl radical, for example, denoting a phenylor benzyl group.

Mention may also be made, for example, of the salts of fatty acids, suchas the salts of oleic, ricinoleic, palmitic and stearic acids, the acidsof coconut oil or of hydrogenated coconut oil; acyllactylates whereinthe acyl radical comprises from 8 to 20 carbon atoms;alkyl-D-galactosideuronic acids and their salts, as well aspolyoxyalkylenated (C₆-C₂₄)alkyl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄)alkylaryl ether carboxylic acids,polyoxyalkylenated (C₈-C₂₄)alkylamido ether carboxylic acids and theirsalts, for example, those comprising from 2 to 50 ethylenic oxidegroups, and mixtures thereof.

nonionic surfactants, among which may be mentioned, alone or asmixtures, for example, polyethoxylated, polypropoxylated orpolyglycerolated fatty alcohols, α-diols, alkylphenols or acids whichhave a fatty chain comprising, for example, from 8 to 18 carbon atoms,it being possible for the number of ethylenic oxide or propylene oxidegroups to range such as from 2 to 50 and it being possible for thenumber of glycerol groups to range such as from 2 to 30.

Mention may also be made, for example, of the copolymers of ethylenicoxide and of propylene oxide and the condensates of ethylenic oxide andof propylene oxide with fatty alcohols; the polyethoxylated fatty amidessuch as having from 2 to 30 mol of ethylenic oxide; the polyglycerolatedfatty amides on average comprising from 1 to 5 glycerol groups and forexample, from 1.5 to 4; the oxyethylenated esters of sorbitan fattyacids having from 2 to 30 mol of ethylenic oxide; the sucrose esters offatty acids, the polyethylene glycol esters of fatty acids,alkylpolyglycosides, the N-alkylglucamine derivatives, or amine oxides,such as the oxides of (C₁₀-C₁₄)alkylamines or theN-acylaminopropylmorpholine oxides.

amphoteric surfactants, among which may be mentioned, alone or asmixtures, derivatives, for example, of aliphatic secondary or tertiaryamines wherein the aliphatic radical is a linear or branched chaincomprising from 8 to 22 carbon atoms and comprising at least onewater-solubilizing anionic group (for example, carboxylate, sulfonate,sulfate, phosphate or phosphonate); mention may also be made, forexample, of (C₈-C₂₀)alkyl betaines, sulfobetaines, (C₈-C₂₀)alkylamido(C₁-C₆)alkyl betaines, such as cocoamidopropyl betaine, or(C₈-C₂₀)alkyl amido(C₁-C₆)alkyl sulfobetaines.

cationic surfactants, among which may be mentioned, for example, aloneor as mixtures, of:

A) the quaternary ammonium salts of the following general formula (XVI):

wherein X is an anion chosen from halides (chloride, bromide or iodide)and (C₂-C₆)alkyl sulfates, such as methyl sulfate, phosphates, alkyl- oralkylarylsulfonates, and anions derived from an organic acid, such asacetate or lactate, and

a) the R₁ to R₃ radicals, which may be identical or different, arechosen from linear and branched aliphatic radicals comprising from 1 to4 carbon atoms and aromatic radicals, such as aryl or alkylaryl. Thealiphatic radicals may comprise heteroatoms, such as, for example,oxygen, nitrogen, sulphur or halogens. The aliphatic radicals are, forexample, chosen from alkyl, alkoxy and alkylamide radicals,

R₄ is chosen from a linear and branched alkyl radical comprising from 16to 30 carbon atoms.

For example, in at least one embodiment, the cationic surfactant is abehenyltrimethylammonium salt (e.g., chloride).

b) the R₁ and R₂ radicals, which may be identical or different, arechosen from linear and branched aliphatic radicals comprising from 1 to4 carbon atoms and aromatic radicals, such as aryl or alkylaryl. Thealiphatic radicals may comprise heteroatoms, such as, oxygen, nitrogen,sulphur or halogens. The aliphatic radicals are, for example, chosenfrom alkyl, alkoxy, alkylamide and hydroxyalkyl radicals comprisingapproximately from 1 to 4 carbon atoms;

R₃ and R₄, which may identical or different, are chosen from linear andbranched alkyl radicals comprising from 12 to 30 carbon atoms, theradical comprising at least one ester or amide functional group.

R₃ and R₄ are chosen, for example, from (C₁₂-C₂₂)alkylamido(C₂-C₆)alkyland (C₁₂-C₂₂)alkyl acetate radicals.

For example, the cationic surfactant is astearamidopropyldimethyl(myristyl acetate)ammonium salt (e.g.,chloride).

B) imidazolinium quaternary ammonium salts, such as, for example, thatof following formula (XVII):

whereinR₅ is chosen from alkenyl and alkyl radicals comprising from 8 to 30carbon atoms, for example derivatives of tallow fatty acids;R₆ is chosen from a hydrogen atom, C₁-C₄ alkyl radicals and alkenyl andalkyl radicals comprising from 8 to 30 carbon atoms;R₇ is chosen from C₁-C₄ alkyl radicals;R₈ is chosen from a hydrogen atom and C₁-C₄ alkyl radicals; andX is an anion chosen from the group of the halides, phosphates,acetates, lactates, alkyl sulfates, and alkyl- and alkylarylsulfonates.R₅ and R₆, in at least one embodiment, are chosen from a mixture ofalkenyl and alkyl radicals comprising from 12 to 21 carbon atoms, suchas derivatives of tallow fatty acids;R₇, for example, comprises methyl; and R₈, for example, compriseshydrogen. Such a product is, for example, Quatemium-27 (CTFA 1997) orQuaternium-83 (CTFA 1997), which are sold under the names “REWOQUAT” W75, W90, W75PG or W75HPG by Witco,

C) di(quaternary ammonium) salts of formula (XVIII):

wherein R₉ is chosen from an aliphatic radical comprising approximatelyfrom 16 to 30 carbon atoms, R₁₀, R′₁₁, R₁₂, R₁₃ and R₁₄, which may beidentical or different, are chosen from hydrogen or alkyl radicalscomprising from 1 to 4 carbon atoms, and X is an anion chosen from thegroup of the halides, acetates, phosphates, nitrates and methylsulfates. Such di(quaternary ammonium) salts comprise, for example,propanetallowediammonium dichloride,

D) quaternary ammonium salts comprising at least one ester functionalgroup of following formula (XIX):

wherein:

-   -   R₁₅ is chosen from C₁-C₆ alkyl radicals and C₁-C₆ hydroxyalkyl        and dihydroxyalkyl radicals;    -   R₁₆ is chosen from:    -   a

-   -    radical        -   saturated and unsaturated, linear and branched,        -   C₁-C₂₂ hydrocarbon radicals R₂₀, and        -   a hydrogen atom,    -   R₁₈ is chosen from:    -   a

-   -    radical saturated and unsaturated, linear and branched, C₁-C₆        hydrocarbon radicals R₂₂, and    -   a hydrogen atom,    -   R₁₇, R₁₉, and R₂₁, which may be identical or different, are        chosen from saturated and unsaturated, linear and branched,        C₇-C₂₂ hydrocarbon radicals;    -   n, p and r, which may be identical or different, are integers        having values ranging from 2 to 6;    -   y is an integer having a value ranging from 1 to 10;    -   x and z, which may be identical or different, are integers        having values ranging from 0 to 10;    -   X is chosen from an organic and inorganic, simple and complex        anion; with the proviso that the sum x+y+z has a value ranging        from 1 to 15, wherein when x has a value of 0, then R₁₆ denotes        R₂₀, and when z has a value of 0, then R₁₈ denotes R₂₂.

The composition according to the disclosure may also compriseingredients commonly used in cosmetics, such as vitamins, fragrances,pearlescent agents, thickeners, gelling agents, trace elements,softening agents, sequestering agents, basifying or acidifying agents,preservatives, sunscreens, antioxidants, agents for combating hair loss,antidandruff agents, propellents, ceramides or their mixtures. Ofcourse, a person skilled in the art will take to choose this or theseoptional additional compounds and/or their amounts so that the desirableproperties of the composition according to the disclosure are not, ornot substantially, detrimentally affected by the envisaged addition.

In another embodiment, the composition according to the disclosurecomprises at least one preservative; as used herein, the term“preservative” refers to any natural or artificial technologicaladditive which has the aim of preserving the cosmetic composition fromany detrimental physicochemical and microbial change. Mention may thusbe made, for example, of:

antimicrobial preservatives: parabens or esters of 4-hydroxybenzoicacid, sorbic acid, 2-phenoxyethanol, formaldehyde, triclosan orquaternary ammoniums, and antioxidizing preservatives: tocopherol orvitamin E, essential oils, ascorbyl palmitate, BHT, BHA or gallates.

The composition according to the disclosure may be provided in the formof a suspension, a dispersion, such as oil in water, by virtue ofvesicles; an optionally thickened, such as gelled, oily solution; anoil-in-water, water-in-oil or multiple emulsion; a gel or a foam; anoily or emulsified gel; a dispersion of vesicles, such as lipidvesicles; a two-phase or multiphase lotion; or a spray. This compositionmay have the appearance of a lotion, of a cream, of an ointment, of asoft paste, of a salve, of a cast or molded solid, such as cast ormolded as a stick or in a dish, or of a compacted solid.

A person skilled in the art may choose the appropriate dosage form, andits method of preparation, on the basis of general knowledge known inthe art, taking into account, on the one hand, the nature of theconstituents used, such as their solubility in the vehicle, and, on theother hand, the application envisaged for the composition.

The cosmetic composition according to the disclosure may be provided inthe form of a product for caring for and/or making up the skin of thebody or face, the lips and the hair, of an antisun or self-tanningproduct, or indeed of a hair product.

For example, the present disclosure may be applicable in the hair field,such as for the form retention of the hairstyle or the shaping of thehair. The hair compositions are, for example, shampoos, gels, hairsetting lotions, blow-drying lotions, or fixing and stylingcompositions, such as lacquers or sprays. The lotions may be packaged invarious forms, such as in vaporizers, pump-action sprays or aerosolcontainers, in order to provide for application of the composition inthe vaporized form or in the foam form.

In another embodiment, the compositions in accordance with thedisclosure may be used for washing or treating keratinous substances,such as the hair, skin, eyelashes, eyebrows, nails, lips or scalp andfor example, the hair.

The compositions according to the disclosure may be detergentcompositions, such as shampoos, shower gels and foam baths. In thisembodiment of the disclosure, the compositions comprise at least onewashing base, generally an aqueous washing base.

The present disclosure further relates to a method for treating, such asfor making up or caring for, keratinous substances, for example, theskin of the body or face, the nails, the hair, including body hair,and/or the eyelashes, comprising applying, to the keratinous substances,a cosmetic composition as defined above.

The application may optionally be followed by rinsing with water. Thus,this method according to the disclosure makes possible the formretention of the hairstyle or the treatment, care or washing of orremoval of makeup from the skin, hair or any other keratinous substance.

The compositions of the disclosure may be further provided in the formof a rinse-out or leave-in conditioner; a perming, hair straightening,dyeing or bleaching compositions; or in the form of rinse-outcompositions, to be applied before or after a dyeing, a bleaching, aperming or a hair straightening or between the two stages of a permingor of a hair straightening.

When the composition is provided in the form of a conditioner optionallyto be rinsed out, it may, for example, comprises at least one cationicsurfactant, such as in a concentration in an amount ranging from 0.1% to10% by weight and for example, from 0.5% to 5% by weight, relative tothe total weight of the composition.

The compositions of the disclosure may also be provided in the form ofwashing composition for the skin and for example, in the form ofsolutions or gels for the bath or shower or of makeup removers.

The compositions according to the disclosure may also be provided in theform of aqueous or aqueous/alcoholic lotions for caring for the skinand/or hair.

The present disclosure is illustrated in more detail in the followingexamples.

Other than in the examples, or where otherwise indicated, all numbersexpressing quantities of ingredients, reaction conditions, and so forthused in the specification and claims are to be understood as beingmodified in all instance by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon desired properties sought to be obtained herein. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should be construed in light of the number of significantdigits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broadscope are approximations, the numerical values set forth in thespecific examples are reported as precisely as possible. Any numericalvalue, however, inherently contain certain errors necessarily resultingfrom the standard deviation found in their respective testingmeasurements.

The following examples are intended to illustrate the present disclosurewithout limiting the scope as a result.

Measurement of the Tg

A film was prepared from a 6% by weight aqueous solution of polymer andwas dried for 48 hours in a controlled atmosphere at 50% relativehumidity and 25° C. The films thus obtained had a thickness ranging from10 μm to 20 μm.

The measuring device is a DSC (TA Instruments).

The sample resulting from the film is placed in a sealed crucible and isheated according to the following protocol:

equilibrium at the starting temperature Ti;

heating 1: increase in the temperature at a rate of +10° C./min up tothe final temperature Tf (° C.);

isotherm lasting 1 minute;

reduction in the temperature at a rate of −10° C./min down to Ti (° C.);

heating 2: increase in the temperature at a rate of +10° C./min up to Tf(° C.);

isotherm lasting 1 minute;

with Ti: Initial temperature −120° C.with Tf: Final temperature +120° C.The Tg values are measured during heating stages 1 and 2.

Measurement of the Water Uptake

Approximately 1 g of dry copolymer is placed in an aluminium dish with adiameter of 4.5 cm (0.01 m²) tared beforehand T. Drying is allowed totake place in an oven at 60° C. under reduced pressure for 48 hours. Thedishes are removed and are immediately weighed (e.g., less than oneminute after being removed from the oven). P1 is obtained.

The dishes are subsequently placed in a glove box having the relativehumidity under consideration (e.g., 75% RH or 85% RH) and are lefttherein for 6 hours. They are subsequently weighed again immediatelyafter being removed from the glove box. P2 is obtained.

The water uptake is calculated in the following way:[(P2−P1)×100]/(P1−T)

EXAMPLE 1

50 ml of methyl ethyl ketone (MEK) were introduced into a (four-necked)reactor equipped with two dropping funnels, a reflux condenser and amechanical stirrer and the reactor was brought to 80° C.

At the same time, a solution 1 comprising 50 g of polyethylene glycolmethacrylate (PEGM 550), 1 g of Trigonox 21S and 75 g of MEK wasprepared.

A solution 2 comprising 75 ml of MEK and 50 g of acrylic acid was alsoprepared.

Solutions 1 and 2 were run into the four-necked reactor simultaneouslyover 30 minutes. The resulting solution was subsequently maintained at80° C. for 5 hours. The orange-yellow solution obtained was cooled. 690ml of 1N sodium hydroxide solution were then added with stirring andthen the solvent (MEK) was evaporated. 95 g of copolymer were obtained.

EXAMPLE 2

In a way similar to Example 1, 50 g of polyethylene glycol methacrylate(PEGM 2000) and 50 g of ammonium sulphatoethyl methacrylate were reactedin 200 ml of water in the presence of 2.5 g of potassium persulphate.This mixture was heated at 70° C. for 4 hours and was then cooled to 25°C. An orange-coloured viscous solution was obtained with a polymercontent of 33% on a dry basis.

EXAMPLE 3

In a way similar to Example 1.75 g of polyethylene glycol methacrylate(PEGM 2000) and 25 g of 3-sulphopropyl acrylate, potassium salt, werereacted in 200 ml of water in the presence of 2.5 g of potassiumpersulphate. This mixture was heated at 70° C. for 4 hours and was thencooled to 25° C. A pale yellow solution was obtained with a polymercontent of 30% on a dry basis.

EXAMPLE 4

In a similar way to Example 1, 75 g of polyethylene glycol methacrylate(PEGM 2000) and 25 g of ammonium sulphatoethyl methacrylate were reactedin 200 ml of water in the presence of 2.5 g of potassium persulphate.This mixture was heated at 70° C. for 4 hours and was then cooled to 25°C. A pale yellow solution was obtained with a polymer content of 33% ona dry basis.

EXAMPLE 5

The water uptakes, at 75% RH and the viscosities (Brookfield viscometer,speed 6 rev/min, 15% by weight solution of polymer in water, at 25° C.,with a rotor of Brookfield No. 1 spindle type, measurement time: 5minutes) of the polymers prepared above were measured.

The results are given in the table below:

Composition of the Solu- Water Viscosity polymer (% by weight) bility*uptake at 15% Example 1 PEGM 550 50% Yes 33% 4 mPa · s Acrylic acid 50%NaOH neutralized 100% Example 2 PEGM 550 50% Yes 73% 333 mPa · sSulphatoethyl methacrylate, ammonium salt, 50% Example 3 PEGM 2000 75%Yes 80% 21 mPa · s 3-Sulphopropyl acrylate, potassium salt, 25% Example4 PEGM 2000 75% Yes 90% 12.1 mPa · s Sulphatoethyl methacrylate,ammonium salt, 25% *“Yes” means that the polymer was soluble in water atleast up to 50% by weight.

EXAMPLE 6

A styling product composition was prepared comprising the followingconstituents (% by weight): 6% of the polymer described in Example 4(with a content of 33% on a dry basis),

preservative, q.s.,

water, q.s. for 100% %.

The styling product composition obtained contributes a good stylingeffect with easy removal on shampooing.

EXAMPLE 7

A shampoo composition was prepared which comprises the followingconstituents (% by weight):

7.5% of lauryl ether sulphate,

2.5% of cocobetaine amphoteric surfactant (Dehyton AB30 from Cognis),

5% of cocopolyglucoside surfactant (Plantacare 818 UP from Cognis),

3% of the polymer described in Example 2 (with a content of 33% on a drybasis),

water, q.s. for 100%.

Good disentangling properties and improved styling were found, in wetand dry surroundings.

What is claimed is:
 1. A random ethylenic copolymer consisting of: a)from 10% to 80% by weight, relative to the total weight of thecopolymer, of at least one monomer chosen from compounds of formula (I):

wherein: R₁ is chosen from a hydrogen atom and linear and branchedhydrocarbon radicals C_(p)H_(2p+1) wherein p is an integer ranging from1 to 12 inclusive; Z is a divalent group chosen from —COO—, —CONH—,—CONCH₃—, —OCO—, —O—, —SO₂—, —CO—O—CO— and —CO—CH₂—CO—; x is chosen from0 and 1; R₂ is chosen from linear, branched and cyclic, saturated andunsaturated, optionally aromatic, divalent hydrocarbon radicals havingfrom 1 to 30 carbon atoms, m is chosen from 0 and 1; n is an integerranging from 3 to 300 inclusive; R₃ is chosen from a hydrogen atom andlinear, branched and cyclic, saturated and unsaturated, optionallyaromatic, hydrocarbon radical with 1 to 30 carbon atoms; and saltsthereof; and b) from 20% to 90% by weight, relative to the total weightof the copolymer, of an anionic monomer, chosen from monomers of formula(II):

wherein: R₁ is chosen from a hydrogen atom and linear and branchedhydrocarbon radicals C_(p)H_(2p+1) wherein p is an integer ranging from1 to 12 inclusive; Z′ is a divalent group chosen from —COO—, —OCO— or—O—, —SO₂—, —CO—O—CO— and —CO—CH₂—CO—; x′ is chosen from 0 and 1; R′₂ ischosen from linear, branched and cyclic, saturated and unsaturated,optionally aromatic, divalent hydrocarbon radicals having 1 to 30 carbonatoms; m′ is chosen from 0 and 1; Y is a group chosen from —SO₃H, and—OSO₃H, and salts thereof.
 2. The copolymer according to claim 1,wherein, in formula (I), R₁ is chosen from hydrogen and from methyl,ethyl, propyl and butyl radicals.
 3. The copolymer according to claim 1,wherein, in formula (I), Z is chosen from —COO— and —CONH—.
 4. Thecopolymer according to claim 1, wherein, in formula (I), R₂ is orcomprises a radical chosen from: an alkylene radical; a phenyleneradical —C₆H₄— (ortho, meta or para) optionally substituted by a C₁-C₁₂alkyl radical; and a benzylene radical —C₆H₄—CH₂— optionally substitutedby a C₁-C₁₂ alkyl radical; a pyridinium radical of the formula:

wherein R′₁ to R′₄, which may be identical or different, are chosen fromH and C₁-C₁₂ alkyl radicals; a radical of formula —CH₂—O—CO—O—,—CH₂—CH₂—O—CO—O—, —CH₂—CO—O—, —CH₂—CH₂—CO—O—, —CH₂—O—CO—NH—,—CH₂—CH₂—O—CO—NH—, —CH₂—NH—CO—NH— and —CH₂—CH₂—NH—CO—NH—, —CH₂—CHOH—,—CH₂—CH₂—CHOH—, —CH₂—CH₂—CH(NH₂)—, —CH₂—CH(NH₂)—, —CH₂—CH₂—CH(NHR′)—,—CH₂—CH(NHR′)—, —CH₂—CH₂—CH(NR′R″)—, —CH₂—CH(NR′R″)—, —CH₂—CH₂—CH₂—NR′—,—CH₂—CH₂—CH₂—O— and —CH₂—CH₂—CHR′—O— wherein R′ and R″ are chosen fromlinear and branched C₁-C₂₂ alkyl; and mixtures thereof.
 5. The copolymeraccording to claim 4, wherein, the alkylene radical is chosen frommethylene, ethylenic, propylene, n-butylene, isobutylene, tert-butylene,n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecyleneand n-docosenylene.
 6. The copolymer according to claim 1, wherein, informula (I), n ranges from 5 to 200 inclusive.
 7. The copolymeraccording to claim 6, wherein, in formula (I), n ranges from 9 to 50inclusive.
 8. The copolymer according to claim 1, wherein, in formula(I), R₃ is chosen from a hydrogen atom; from mesityl, tosyl,triethoxysilyl, and —CH₂—CH₂CN radicals; from benzyl and phenyl radicalsoptionally substituted by a C₁-C₁₂ alkyl radical; and C₁-C₃₀ alkylradicals from glutarate, mesityl, benzoate, tosyl, triethoxysilane,thioester, benzotriazole carbonate, butyraldehyde, acetaldehyde diethylacetal, biotin, phospholipid —SO₃H, —COOH, and —PO₄.
 9. The copolymeraccording to claim 1, wherein the monomer of formula (I) is chosen from:polyethylene glycol (meth)acrylate; methylpolyethylene glycol(meth)acrylate; alkylpolyethylene glycol (meth)acrylates;phenylpolyethylene glycol (meth)acrylate; a monomer of:

wherein n ranges from 3 to 100 inclusive, and mixtures thereof.
 10. Thecopolymer according to claim 9, wherein n ranges from 7 to 30 inclusive.11. The copolymer according to claim 1, wherein the at least one monomeris present in an amount ranging from 20% to 70% by weight, relative tothe total weight of the copolymer.
 12. The copolymer according to claim1, wherein the at least one monomer is present in an amount ranging from30% to 60% by weight, relative to the total weight of the copolymer. 13.The copolymer according to claim 1, wherein, in formula (II), R₁ ischosen from hydrogen and from methyl, ethyl, propyl and butyl radicals.14. The copolymer according to claim 1, wherein, in formula (II), Z′ isCOO.
 15. The copolymer according to claim 1, wherein, in formula (II),R′₂ is or comprises a radical chosen from: an alkylene radical; aphenylene radical —C₆H₄— (ortho, meta or para) optionally substituted bya C₁-C₁₂ alkyl radical; and a benzylene radical —C₆H₄—CH₂— optionallysubstituted by a C₁-C₁₂ alkyl radical; a radical of formula—CH₂—O—CO—O—, —CH₂—CH₂—O—CO—O—, —CH₂—CO—O—, —CH₂—CH₂—CO—O—,—CH₂—O—CO—NH—, —CH₂—CH₂—O—CO—NH—, —CH₂—NH—CO—NH—, and—CH₂—CH₂—NH—CO—NH—, —CH₂—CHOH—, —CH₂—CH₂—CHOH—, —CH₂—CH₂—CH—O— and—CH₂—CH₂—CHR′—O— wherein R′ is chosen from linear and branched C₁-C₂₂alkyl radicals; and mixtures thereof.
 16. The copolymer according toclaim 15, wherein, the alkylene radical is chosen from methylene,ethylenic, propylene, n-butylene, isobutylene, tert-butylene,n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecyleneand n-docosenylene.
 17. The copolymer according to claim 1, wherein, theat least one anionic monomer is chosen from styrenesulphonic acid,sulphopropyl (meth)acrylate, sulphatoethyl (meth)acrylate and saltsthereof.
 18. The copolymer according to claim 17, wherein the saltsthereof comprise ammonium salts.
 19. The copolymer according to claim 1,wherein the at least one anionic monomer is present in an amount rangingfrom 30% to 80% by weight, relative to the total weight of thecopolymer.
 20. The copolymer according to claim 1, wherein the at leastone anionic monomer is present in an amount ranging from 40% to 70% byweight, relative to the total weight of the copolymer.
 21. The copolymeraccording to claim 1, wherein the copolymer exhibits a weight-averagemolecular mass (Mw) ranging from 500 to 5,000,000.
 22. The copolymeraccording to claim 1, wherein the copolymer exhibits a weight-averagemolecular mass (Mw) ranging from 8,000 to 100,000.
 23. The copolymeraccording to claim 1, wherein the copolymer is conveyed in an aqueousmedium.
 24. The copolymer according to claim 23, wherein the aqueousmedium is water-soluble or water-dispersible.
 25. The copolymeraccordingly to claim 1, wherein the copolymer exhibits a viscosity inwater ranging from 1 mPa·s to 1000 mPa·s, measured at 25° C.
 26. Thecopolymer accordingly to claim 25, wherein the copolymer exhibits aviscosity in water ranging from 2 mPa·s to 500 mPa·s, measured at 25° C.27. The copolymer according to claim 1, wherein the copolymer exhibits aglass transition temperature (Tg) ranging from −150° C. to 20° C. 28.The copolymer according to claim 1, wherein the copolymer exhibits aglass transition temperature (Tg) ranging from −100° C. to 0° C.
 29. Thecopolymer according to claim 1, wherein the copolymer exhibits a wateruptake ranging from 3% to 150% by weight, at 75% relative humidity (75%RH), and/or the copolymer exhibits a water uptake ranging from 5% to 90%by weight, at 85% relative humidity (85% RH).
 30. The copolymeraccording to claim 1, wherein the copolymer exhibits a water uptakeranging from 4.5% to 90% by weight, at 75% relative humidity (75% RH),and/or the copolymer exhibits a water uptake ranging from 15% to 60% byweight, at 85% relative humidity (85% RH).
 31. The copolymer accordingto claim 1, wherein the copolymer has an overall negative charge.
 32. Acosmetic or pharmaceutical composition comprising, in a physiologicallyacceptable medium, from 0.1% to 30% by weight on a dry basis, relativeto the total weight of the composition of at least one random ethyleniccopolymer according to claim
 1. 33. A method for treating hair whichcomprises applying to the hair, a cosmetic composition comprising, in aphysiologically acceptable medium, at least one random ethyleniccopolymer according to claim
 1. 34. A random copolymer consisting of: a)from 10% to 80% by weight, relative to the total weight of thecopolymer, of at least one monomer chosen from compounds of formula (I):

wherein: R₁ is chosen from a hydrogen atom and linear and branchedhydrocarbon radicals of C_(p)H_(2p+1) wherein p is an integer rangingfrom 1 to 12 inclusive; Z is a divalent group chosen from —COO—, —CONH—,—CONCH₃—, —OCO—, —O—, —SO₂—, —CO—O—CO— and —CO—CH₂—CO—; x is chosen from0 and 1; R₂ is chosen from linear, branched and cyclic, saturated andunsaturated, optionally aromatic, divalent hydrocarbon radicals havingfrom 1 to 30 carbon atoms; m is 0 or 1; n is an integer ranging from 3to 300 inclusive; R₃ is chosen from a hydrogen atom and linear, branchedand cyclic, saturated and unsaturated, optionally aromatic, hydrocarbonradical with 1 to 30 carbon atoms; and salts thereof; and b) from 20%to-90% by weight, relative to the total weight of the copolymer, of ananionic monomer, chosen from monomers of formula (II):

wherein: R₁ is chosen from a hydrogen atom and linear and branchedhydrocarbon radicals C_(p)H_(2p+1) wherein p is an integer ranging from1 to 12 inclusive; Z′ is a divalent group chosen from —COO—, —OCO— or—O—, —SO₂—, —CO—O—CO— and —CO—CH₂—CO—; x′ is chosen from 0 and 1; R′₂ ischosen from linear, branched and cyclic, saturated and unsaturated,optionally aromatic, divalent hydrocarbon radicals having 1 to 30 carbonatoms; m′ is chosen from 0 and 1; Y is a group chosen from —SO₃H, and—OSO₃H and salts thereof, and optionally at least one additionalnonionic hydrophilic monomer chosen from monomers of formula (III):

wherein: R″₁ is chosen from a hydrogen atom and —CH₃; Z″ is a divalentgroup chosen from —COO—, —CONH—, —CONCH₃—, —OCO—, —SO₂—, —CO—O—CO—,—CO—CH₂—CO— or —O—; preferably —COO— and —CONH—; x″ is chosen from 0 and1; and R″ is chosen from linear, branched and cyclic, saturated andunsaturated, optionally aromatic, hydrocarbon radical with 1 to 30carbon atoms.
 35. A cosmetic or pharmaceutical composition comprising,in a physiologically acceptable medium, from 0.1% to 30% by weight on adry basis, relative to the total weight of the composition of at leastone random ethylenic copolymer according to claim
 34. 36. A method fortreating hair which comprises applying to the hair, a cosmeticcomposition comprising, in a physiologically acceptable medium, at leastone random ethylenic copolymer according to claim 34.